Polyphosphorus esters and method of preparing same



3,014,954 POLYPHOSPHORUS ESTERS F PREPARING SAME Gail H. Birum, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed June 16, 1959, Ser. No. 820,618 16 Claims. (Cl. 260-461) NETHOD wherein R is selected from the class consisting of alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxyalkyl, aryloxyalkyl, alkoxyhaloalkyl and aryloxyhaloalkyl radicals of from 1 to 12 carbon atoms, R is selected from the class consisting of OR and aromatic hydrocarbyl and halohydrocarbyl radicals of from 6 to 12 carbon atoms, Z is selected from the class consisting of hydrogen and hydrocarbyl, halohydrocarbyl, carboalkoxyhydrocarbyl, alkylthiohydrocarbyl, alkoxyhydrocarbyl, and cyanohydrocarbyl radicals of from 1 to 17 carbon atoms, and the furyl and thienyl radicals and n is a number of at least 1.

According to the invention, compounds of the above formula are readily prepared by reacting together a trivalent phosphorus ester with an aldehyde and an organic phosphorus compound having halogen attached to the phosphorus atom thereof, the ratio of the three reactants being such that the aldehyde and halogen compound are present in substantially equimolar proportions and the trivalent phosphorus ester is present in lessthan an equirnolar proportion with respect to the other two reactants. Upon mixing together the three reactants in the 1:111 proportion, there is probably first formed a trivalent phosphorus ester of a hydroxy pentavalent phosphorus ester, e.g., one of the classes of compounds disclosed in my copending application, Serial No. 780,209, filed December 15, 1958, now abandoned, and in application, Serial No. 27,505, filed May 9, 1960, which application is a continuation-in-part of said abandoned application. It is formed according to the scheme:

it ROPX-i- H-FREPOR- RO?O-?HIR'+RX ia' l R z B wherein R, R, and Z are defined above, and X is selected from the class consisting of chlorine and bromine. The reaction schematically shown above results in depletion of the phosphorus ester R' POR since it was present in the initial reaction mixture in a quantity which was less than equimolar based on the halogen compound and on the aldehyde. Unreacted halogen compound and unreacted aldehyde are still present, however, and they react with the reaction product (I), according to the scheme:

3,014,954 Patented Dec. 26, 1961 The compound (II) can then react with a trivalent phosphorus halogen compound and an aldehyde in the way that compound (I) or the compound R' POR do. It thus reacts as follows:

' L w ll l From the above, it is apparent that the presence of repeating units 0 [-0 OHl :l

in a product prepared from the ester R' POR, the phosphorohalidite and the aldehyde, depends upon whether the quantity of the phosphite present in the initial reaction mixture is less on a molar basis than the quantity of phosphorohalidite or phosphonohalidite and aldehyde. Whenever it is less, the 1:1:1 reaction product functions as a trivalent phosphorus ester R' POR, and reacts with the excess of halidite and aldehyde present. The product thus formed in turn functions as a trivalent phosphorus ester, so that the presently provided method in effect involves a chain reaction to give a mixture of compounds having varying proportions of the repeating unit 0 [own] The compound which is formed from a 1:1:1 molar mixture of the trivalent phosphorus halogen compound, the aldehyde and the trivalent phosphorus ester is a phosphite-phosphonate when the ester and the halidite are derived from phosphorous acid, thus:

0 RO-IX+% JH+P(OR)s- ROIFO?HIi OR-I-RX OR Z OR Z B When the ester and the halidite are derived from a hydrocarbylor halohydrocarbylphosphonous acid, the 1:1:1 product is a phosphonite-phosphinate, thus:

where Y is a hydrocarbyl or halohydrocarbyl radical.

When the ester is derived from phosphorous acid and the halidite is derived from a phosphonous acid the 1:1:1 product is a phosphonite-phosphonate, thus:

When the ester is derived from a phosphonous acid and the halidite is derived from phosphorous acid, the product is a phosphite-phosphinate, thus:

When the ester is derived from phosphinous acid and the halidite is derived from a phosphorous acid, the product is a phosphite-phosphine oxide:

(Ro)PX+( |iH+Ro-1 Y-v(R)P0?Hi -Y+R01 z Y z Y Similarly with the same ester and a phosphonohalidite instead of the phosphorohalidite, the product is a phosphonite-phosphine oxide:

ll i1 R0fiX+(fH+RO?-Y RO?O EH$Y Y z Y Y z Y The 1:1:1 reaction products are thus phosphite-phosphonates, phosphonite-phosphinates, phosphonite-phosphonates, phosphite phosphinates, phosphite phosphine oxides, or phosphonite-phosphine oxides. There is always present one trivalent phosphorus ester group and one pentavalent phosphorus ester group. The unit which is introduced into the 1:1:1 molecule by reaction with an aldehyde and a trivalent phosphorus halide always has a pentavalent phosphorus atom, and the R is always derived from the phosphorus halogen compound, being the oxy group OR when the halogen compound is derived from phosphorous acid or the hydrocarbyl or halohydrocarbyl radical Y when the halogen compound is derived from a phosphonous acid. The presently provided compounds are thus compounds having a single trivalent phosphorus ester radical and a plurality of penta valent phosphorus ester radicals. One such pentavalent radical is present, of course, in the 1:1:1 reaction product. The number of the additional pentavalent phosphorus ester groups is a function of the quantity of phosphorus halogen compound and aldehyde available. When these are present only in small excess with respect to the originally employed trivalent phosphorus ester, the reaction mixture will consist primarily of the 1:1:1 product, with minor proportions of compounds having one or more of the groups As the excess of halogen compound and the aldehyde in the initial reaction mixture increases, or more halogen compound and aldehyde are added to the reaction mixture, the final product contains increasingly greater quantities of compounds having a plurality of pentavalent phosphorus ester groups, i.e., phosphonate or phosphinate radicals. Depending upon the available phosphorus halogen compound and the available aldehyde, a great many pentavalent phosphorus ester units can be introduced into the 1:1:1 product. Generally speaking the polyphosphonate or polyphosphinate product will consist of a mixture of compounds having a varying number, say, from 1 to of the phosphonate or phosphinate units in addition to that present in the 1:1:1 reaction product. Mixtures comprising the 1:1:1 reaction products and the polyphosphonates or polyphosphinates may be used as such for a wide variety of commercial and agricultural purposes. However, if desired, the 1:1:1 products can be removed by isolating procedures customarily employed by those skilled in the art, e.g., by distillation, solvent extraction, etc. Also narrow cuts of the higher ratio products can be obtained by techniques such as molecular distillation, chromatography, etc.

Although a convenient means of preparing the present polyphosphonates or polyphosphinates comprises employing, in an initial reaction mixture, less than an equimolar quantity of trivalent phosphorus ester with respect to the phosphorus halide and aldehyde, the present polyphosphonates or polyphosphinates can also be prepared by starting with a previously prepared 1:1:1 reaction product and adding the phosphorus halide and the carbonyl compound thereto. Thus, from a 1:1:1 mixture of a phosphorus halogen compound such as dimethyl phosphorochloridite, an aldehyde such as propionaldehyde and a trivalent phosphorus ester such as triethyl phosphite there is obtained, according to the process of said copending application, Serial No. 780,209, the dimethyl phosphite of diethyl 1-hydroxypropylphosphonate:

This compound can then be converted to one having a plurality of pentavalent phosphorus radicals by reacting it with additional quantities of the dimethyl phosphorochloridite and of the propionaldehyde to give the phoswhere n is at least one. Or, instead of using the same trivalent phosphorus halide and the same aldehyde which was used for preparing the dimethyl phosphite of diethyl l-hydroxypropylphosphonate, there may be used a different trivalent phosphorus halide, e.g., 2-chloroethyl ethylphosphonochloridite and a different aldehyde, e.g., benzaldehyde. In this case, the reaction proceeds as follows:

CHnCHzO CH:

CHaO CHICHI CHzCH:

O CH: O

It is thus apparent that in the repeating units the substituents Z and R need not be the same radical in all of the units of the poly phosphorus ester. The present invention thus provides a great diversity of compounds having a single trivalent phosphorus radical and plurality of pentavalent phosphorus radicals.

The invention is particularly suited to the production of phosphite-polyphosphonates from mixtures consisting of bis(haloalkyl) phosphorohalidites and less than an equimolar proportion of tris(haloalkyl) phosphites which mixtures are readily obtainable by reaction of a phosphorus trihalide with an olefin oxide in certain ratios. As disclosed in my copending application, Serial No. 780,262, filed December 15, 1958, the reaction of two moles of phosphorus trichloride or phosphorus tribromide with five moles of an olefin oxide, e.g., ethylene oxide, results in the production of an equimolar mixture of a phosphorochloridite and a tribasic phosphite, thus:

However, when there is used with the two moles of phosphorus trichloride a quantity .of alkylene oxide which is less than five moles, but greater than four moles, the reaction product contains less of tribasic phosphite than of phosphorochloridite. 'For example, using 2 moles of phosphorus trihalide and 4.98 moles of alkylene oxide, the reaction product consists essentially of 0.9 8 mole of tribasic phosphite and 1.02 moles of phosphorohalidite. Using 2 moles of phosphorus trihalide and 4.95 moles of alkylene oxide, the reaction product consists of about 0.95 mole of phosphite and 1.05 moles of the halidite. As the number of moles of the alkylene oxide per 2 moles of phosphorus trichloride approaches 4, there is an increasingly greater content of phosphorohalidite in the reaction product. The variation of halidite to ester ratio in the reaction product of an alkylene oxide and phosphorus trihalide is shown below.

Moles of Moles of alkylene oxide halidite in per 2 moles of product per P01 or PBr; mole of phosphite The average number of the units in the polyphosphorus compounds obtained by reacting the phosphite-halidite mixture with an aldehyde in a quantity which is at least equimolar with respect to the halidite increases with increasing halidite ratio. When the phosphite to halidite ratio is 0.98:1.02, the reaction product consists of about 96% on a molar basis of the 1:1:1 halidite-aldehyde-ester compound (which has none such unit) and about 4% on a molar basis of a compound having one such unit. When the phosphite to halidite ratio is 0.95 :1:1.05, the reaction product consists of about 89.5% on a molar basis of a compound having none such units and about 10.5% on a molar basis of a compound having one such unit. As the halidite content of the phosphorus trichloride-alkylene oxide reaction product increases, the number of said units in the product obtained therefrom by reaction with an aldehyde increases, as is apparent from the table It will thus be noted that as the halidite content of the phosphorus trichloride-alkylene oxide reaction mixture increases, the number of said units in the polyphosphorus compounds appears to increase asymptotically. Thus from a 1:101 phosphite-halidite mixture, the calculated average number of said units in the polyphosphorus compound is 100. For practical purposes and in order to obtain products of value for presently desired industrial application, it is preferred to operate in such a manner that the average number of said units is, say, from 1 to 10, and more advantageously from 1 to 4.

As will be apparent to those skilled in the art, the term average units when applied to repetitive portions of a high molecular weight composition indicates a mixture in which there is present varying numbers of such units. Hence, in a composition which is stated to have, say, an average of 10 repeating units there will be present compounds having less than 10 such units as well as compounds having more than 10 units.

It is thus apparent that so long as there is employed in the reaction with the aldehyde a mixture of phosphorohalidite and tribasic phosphite which is prepared by addition of two moles of phosphorus trihalide with more than four, but less than five moles of alkylene oxide, and the quantity of aldehyde used is at least equimolar with respect to the phosphorohalidite content of the so obtained phosphorus trichloride-alkylene oxide reaction product, there is present in the final reaction product a substantial quantity of phosphite-polyphosphonate.

As hereinbefore disclosed, the trivalent phosphorus halogen components which are generally useful in preparing the presently provided polyphosphonate or polyphosphinate compounds have the general formula ROPX wherein R is selected from the class consisting of alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxyalkyl, aryloxyalkyl, alkoxyhaloalkyl, and aryloxyhaloalkyl radicals of from 1 to 12 carbon atoms, R is selected from the class consisting of OR and hydrocarbyl and halohydrocarbyl radicals of from 1 to 12 carbon atoms and X is selected from the class consisting of chlorine and bromine.

An important class of phosphorus halogen compounds of the above formula are the phosphorohalidites, i.e., compounds of the formula (RO) PX. This includes the alkyl or alkenyl phosphorochloridites or phosphorobromidites, e.g., dimethyl, diethyl, diisopropyl, di-n-propyl, diisobutyl, di-n-butyl, di-n-amyl, di-n-hexyl, di-n-heptyl, di-n-octyl, bis(2-ethylhexyl), di-tert-nonyl, didecyl, diundecyl, di-n-dodecyl, bis(2-butyloctyl), di-tert-dodecyl, divinyl, diallyl, di-Z-butenyl, di-Z-pentenyl, dioctenyl, didodecenyl, allyl butyl, ethyl methyl, isohexyl methyl, dodecenyl ethyl and Z-ethylhexyl n-propyl phosphorochloridite or phosphorobromidite. Particularly useful are the haloalkyl phosphorohalidites, e.g., bis(Z-chloroethyl), bis(2,3-dichloropropyl), bis (2-bron1opropyl), bis(2- bromo 3 chloropropyl), bis( 3 bromo-Z-chloropropyl), bis(tetrachlorobutyl), bis(2-chloropropyl), bis(dichloroamyl), bis(dichlorododecyl), 2-chloroethyl methyl, allyl 2-brornopropyl, dibromohexyl butenyl or 2-chloropropyl dodecyl phosphorochloridite or phosphorobromidite. Also presently useful are the alkoxyalkyl or aryloxyalkyl phosphorohalidites such as bis(Z-methoxyethyl), bis(2- ethoxyethyl), bis(4-butoxybutyl), bis(butoxyoctyl), 2- ethoxyethyl dodecyl, bis(3-ethoxypropyl), 2-ethoxyethyl 2-chloroethyl, allyl 4-rnethoxybutyl, bis(Z-phenoxyethyl), bis[3-(B-naphthloxypropyl) bis [4-(p-tolyloxy) butyl] 2- propoxyethyl 2-phenoxyethyl, and 3-(4-ethylphenoxy)- propyl 2-bromoethyl phosphorochloridite or phosphorobrornidite.

Also useful are the haloalkenyl phosphorohalidites e.g. the bis(2-chloro-3-pentenyl) phosphorochloridite obtained by reaction of phosphorus trichloride with 4,5- epoXy-2-pentene.

The alkoxyhaloalkyl or aryloxyhaloalkyl phosphorochloridites'obtained by reaction of glycidyl ethers with phosphorus trichloride or phosphorus tribromide are likewise very useful phosphorus-halogen reactants, as will be hereinafter disclosed.

Also useful in the reaction with aldehydes and triorgano phosphites to give the present poly phosphorus compounds are the esters of hydrocarbylor halohydrocarbylphosphonohalidites, i.e., compounds of the formula wherein R is as above defined and Y denotes a hydrocarbyl or halohydrocarbyl radical of from 1 to 12 carbon atoms.

Presently useful hydrocarbylphosphonohalidites or halohydrocarbylphosphonohalidites include, e.g.,

methyl phenylphosphonochloridite,

ethyl a-naphthylphosphonochloridite,

ethyl 2-fiuo1'oethylphosphonochloridite,

2-ethoxyethyl methylphosphonobromidite,

n-butyl benzylphosphonochloridite,

n-amyl p-tolylphosphonobromidite,

isopropyl cyclohexylphosphonochloridite,

3-ethoxy-2-chloropropyl 2,4-diethylphenylphosphonobromidite,

3-phenoxypropyl 2,3-dichlorophenylphosphonochloridite,

2-fluoroethyl n-butylphosphonochloridite,

2-butyloctyl n-propylphosphonochloridite,

methyl or-chlorobenzylphosphonochloridite,

amyl decylphosphonochloridite,

2-bromo-4-ethoxybutyl p-biphenylphosphonochloridite,

undecyl n-hexylphosphonobromidite,

ethyl tetrachlorobutylphosphonochloridite,

n-hexyl Z-methylcyclopentylphosphonobromidite,

ethyl 4-n-hexylphenylphosphonochloridite,

allyl Z-phenylethylphosphonochloridite,

2-bromo-3-hexenyl phenylphosphonochloridite,

n-dodecyl 2-ethylhexylphosphonochloridite,

2-chlor0ethyl phenylphosphonochloridite,

tetrachloropentyl ethylphosphonochloridite,

3-bromopropyl n-hexylphosphonochloridite,

2-bromopropyl ,B-bromo-a-naphthylphosphonobromidite,

dibromododecyl methylphosphonobromidite,

Z-iodoethyl benzylphosphonochloridite,

n-octyl 4-iodophenylphosphonochloridite,

trichlorooctyl cyclohexylphosphonochloridite,

4-fiu0robutyl a-naphthylphosphonochloridite, ethyl 3-butenylphosphonochloridite,

2-chloropropyl 2-hexenylphosphonochloridite,

2-chloro-4-ethoxybutyl n-butylphosphonochloridite, etc.

Any of the above described trivalent phosphorus halogen compounds can be reacted with an equimolar amount of an aldehyde and a triorgano phosphite in less than equimolar quantity to give the presently provided poly phosphorus compounds.

The useful adehydes have the formula ZCHO wherein Z is selected from the class consisting of hydrogen and hydrocarbyl, halohydrocarbyl, carboalkoxyhydrocarbyl, alkylthiohydrocarbyl, alkoxyhydrocarbyl and cyanohydrocarbyl radicals of from 1 to 12 carbon atoms, and the thienyl and furyl radicals.

Owing to their easy availability, a particularly useful class of aldehydes includes the aliphatic hydrocarbon aldehydes of from 1 to 18 carbon atoms, e.g., formaldehyde, acetaldehyde, acrolein, propionaldehyde, butyraldehyde, isovaleraldehyde, hexanal, citronellal, heptanal, tiglic aldehyde, Z-ethylhexanal, octanal, 2-butyloctanal, prepargaldehyde, 6-methylheptanal, amylpropiolic aldehyde, decanal, undecanal, 2-methylundecanal, lauraldehyde, stearaldehyde, tridecaldehyde, etc.

The presence of cyano, halogen, alkyl, carboalkoxy, alkoxy and alkylthio-substituents in the aliphatic aldehyde has no effect on the course of the reaction; hence, there may be employed such substituted fatty aldehydes as 3-cyanopropionaldehyde, chloroacetaldehyde, 3-butoxybutyraldehyde, 4-cyano-2,2-dimethyl butyraldehyde, 2,3-dichloropropionaldehyde, chloral, 3-isopropoxypropionaldehyde, 3-(ethylthio) 3 methylbutyraldehyde, 2- methyl-3 fluoropropionaldehyde, dibromostearaldehyde, dichlorolauraldehyde ethyl ll-formylundecanoate, succinaldehydic acid methyl ester, ethyl 4-formylbutyrate, diethyl formylsuccinate, iodoacetaldehyde, dichloroacetaldehyde, etc.

Presently useful alicyclic carboxaldehydes include cyclohexanecarboxaldehyde, 6 methyl 3 cyclohexenecarboxaldehyde, 2-cyclohexene-l-carboxaldehyde, cyclopentanecarboxaldehyde, 3-isopropyl-l-methylcyclohexanecarboxaldehyde, 5 ethoxy-Z-cyclopentene-l-carboxaldehyde, 1 bromo 2,2,6 trimethylcyclohexanecarboxaldehyde, 2,2,6 trimethylcyclohexanecarboxaldehyde, 2,2,6 trimethyl-Z-cyclohexenecarboxaldehyde, 4 chlorocyclohexanecarboxaldehyde, etc. The heterocyclic aldehydes includes furfural and the thiophenecarboxaldehydes.

The presently useful benzenoid aldehydes may be aliphatic-aromatic or purely aromatic aldehydes which may or may not be further substituted, e.g., benzaldehyde, o-, mor p-tolualdehyde, phenylacetaldehyde, dipentylbenzaldehyde, cinnamaldehyde, 1- or 2-napl1thaldehyde, biphenyl-4-carboxaldehyde, ot-phenylacrolein hydrocinnamaldehyde, 2,3-dichlorobenzaldehyde, phenylpropargaldehyde, 2-, 3- or 4-butoxybenzaldehyde, 0-, mor p-chlorobenzaldehyde, p-(ethoxy)benzaldehyde, 2-ethoxybenzaldehyde, 3,4-dipropoxybenzaldehyde, 4-(n-butylthio)ber1- zaldehyde, o-, mor p-iodobenzaldehyde, 3,4- or 3,5-dibromobenzaldehyde, S-tert-butyl-m-tolualdehyde, S-tertbutyl-3-fiuoro-o-tolualdehyde, Z-p-cymenecarhoxaldehyde, 6-methoxy-2-naphthaldehyde, 2-butoxy-l-naphthaldehyde, 4'-bromo-4-biphenylcarboxaldehyde, etc.

Triorgano phosphites which are generally useful with the aldehyde and the phosphorus halide, according to the invention, are either simple or mixed phosphites. Examples of useful phosphites are trimethyl, triethyl, triallyl, triisopropyl, tri-n-propyl, tri-Z-butenyl, tri-n-butyl, tri-tert-amyl, tri-n-hexyl, tri-n-heptyl, tris(Z-ethylhexyl), trioctenyl, tri-n-octyl, trinonyl, tridecyl, triundecyl, tritert-dodecyl, tridodecenyl, amyl diethyl, butyl dl-n-propyl, n-dodecyl dimethyl, ethyl octyl propyl, tris(Z-chloroethyl), tris(3-chloropropyl), tris(Z-chloropropyl), tris- (3,4-dichlorobutyl), tris(3-chloro-4-pentenyl), tris(2- bromethyl) tris 3-chloro-2-propenyl) tris 3-iodopropyl tris(Z-fluoroethyl), tris(dichlorododecyl), tris(2-ethoxyethyl), 2-chloroethyl diethyl, tris(3-phenoxypropyl), 3- bromopropyl, bis(2-chloroethyl), diamyl trichlorooctyl, 2-chloroethyl 3-chloropropyl 4-chlorobutyl, 2-chloroethy1 methyl propyl, tris(2,3-dichloropropyl), tris(2-bromo- 3-chloropropyl), tris(3-bromo-2-chloropropyl), tris(Z- chloro-3-methoxypropyl) and tris(2-bromo-4-phenoxybutyl) phosphite.

Instead of the tribasic phosphites there may be employed as the trivalent phosphorus ester component a diester of a hydrocarbyl or halohydrocarbylphosphonite, i.e., a compound of the formula YP(OR) Where Y is selected from the class consisting of hydrocarbyl and halohydrocarbyl radicals of from 1 to 12 carbon atoms.

Presently useful phosphonites include, e.g., dimethyl phenylphosphonite, diethyl 2-propenylphosphonite, ethyl methyl phenylphosphonite, di-n-propyl methylphosphonite, di-n-butyl benzylphosphonite, bis(Z-chloroethyl) p-tolylphosphonite, bis(2-methoxyethyl) cyclohexylphosphonite, bis(Z-ethylhexyl) 2,4-diethylphenylphosphonite, bis(Z-bromo-S-ethoxypropyl) 2 bromoethylphosphonite, diethyl 2-propinylphosphonite, bis(Z-butyloctyl) 2-butenylphosphonite, di-n-hexyl p-biphenylphosphonite, diundecyl n-hexylphosphonite, bis(trichloropropyl) 2- methylcyclopentylphosphonite, diethyl 4-n-hexylphenylphosphonite, diallyl 2-phenylethylphosphonite, dipentenyl 2-ethylhexylphosphonite, bis(Z-chloroethyl) phenylphosphonite, bis(tetrachloropentyl) ethylphosphonite, bis(3- bromopropyl) biphenylylphosphonite, bis(2-chloro-4- phenoxybutyl) methylphosphonite, 2-iodoethyl Z-bromo- 3-chloropropyl phenylphosphonite, allyl propyl 2,4-dichlorophenylphosphonite, bis(trichlorooctyl) cyclohexyl phosphonite, bis(4-fluorobutyl) Z-cyclohexenylphosphonite, bis(4-chlorobutyl) ethylphosphonite, bis(dichlorohexyl) phenylphosphonite, bis(Z-chloropropyl) n-butylphosphonite, di-n-butyl pentachlorophenylphosphonite, etc.-

vPresently useful as the ester component are also phosphinites of the formula Y POR wherein Y and R are as herein defined, e.g., the alkyl or alkenyl dihydrocarbylphosphinites such as ethyl, allyl, butyl, n-octyl diethylphosphinite or diphenylphosphinite, benzylcyclohexylphosphinite or dia-llylphosphinite; the corresponding haloalkyl esters such as 2-chloropropy1 di-p-tolphosphinite or 2-fluoroethyl ethylmethylphosphinite; the ether-substituted esters such as 4-methoxybutyl or 3-phenoxy-2- chloropropyl di-n-butylphosphinite or di-B-naphthylphosphinite; and the corresponding esters of the halo-substituted phosphinic acids such as the methyl, pentyl, ethyl, Z-butenyl, 2-chloroethyl, 3-ethoxypropyl, or 4-butoxy-2- bromopentyl esters of bis(Z-chloropropyl) phosphinite or of n-butyl(4-chlorophenyl)phosphinite.

The alkyl radical of a trialkyl phosphite, of a dialkyl halohydrocarbylphosphonite, of a dialkyl hydrocarbylphosphonite, or of an alkyl dihydrocarbylphosphinite and halo derivatives thereof may also be one derived from a branched chain alcohol obtained according to the x0 process by the reaction of carbon monoxide and hydrogen with a higher olefin, e.g., butylene dimer or propylene trimer.

As has been herein disclosed, the present invention is particularly suited to the production of phosphite-polyphosphonates from the mixtures of a phosphorochloridite or phosphorobromidite and less than an equimolar quantity of a triorgano phosphite which are obtained by reacting two moles of phosphorus trichloride or phosphorus tribromide with more than four moles but less than five moles of an oxirane compound e.g., an alkylene oxide.

Oxirane compounds suitable for reaction with the phosphorus trichloride or phosphorus tribromide to yield the mixtures of phosphite and phosphorochloridite are e.g., ethylene oxide and alkyl derivatives thereof such as propylene oxide, isobutylene oxide, 1,2-epoxybutane, 2,3- epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 2,3- epoxyhexane, 1,2-epoxyhexane, 1,2-epoxyheptane, 2,3- epoxy-3-ethylpentane, 1,2-epoxy-4-methylpentane, 1,2- epoxy-Z-ethylhexane, l-2-epoxy-2,4,4 trimethylpentane, 1,2-epoxy-2,3-dimethylheptane, haloalkyl-substituted oxiranes such as epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin, 1,2-epoxy-4-bromobutane, 2,3-

epoxy-4-chlorobutane, 1,2-epoxy-3,4 dibromobutane, 2,3- epoxy-l-bromopentane, 3,4-epoxy-2-chlorohexane, 1,2- epoxy-3,3,3-trifiuoropropane, 1-bromo-2,3-epoxyheptane; the alkenyl-substituted oxiranes such as 3,4-epoxy-4- methyl-l-pentene and 3,4-epoxy-l-butene; aryl-substituted oxiranes such as (epoxyethyl)benzene, (1,2-epoxy-lmethylethyDbenzene, (3-chloro-1,2-epoxypropyl)benzene and (1,2-epoxypropyl)benzene; alkoxyalkyland phenoxyalkyl-substituted oxiranes such as the methyl, ethyl, isopropyl, isoamyl and phenyl ethers of glycidol, i.e., compounds of the formula C H z CHOHzOR where R is methyl, ethyl, isopropyl, amyl or phenyl; (Z-ethoxyethyDethylene oxide, etc.

Reaction of two moles of phosphorus trichloride or of phosphorus tribromide with more than four but less than five moles of the useful oxiranes gives, by way of example, mixtures of the following phosphites and phosphorohalidites wherein the latter is present in molar excess:

(1) Tris(Z-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite (II) Tris(2,3-dichloropropyl) phosphite and bis(2,3-dichloropropyl) phosphorochloridite (III) Tris(Z-chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite (IV) Tris(Z-bromoethyl) phosphite and bis(Z-bromoethyl) phosphorobromidite (V) Tris(Z-bromopropyl) phosphite and bis(Z-brdmopropyl) phosphorobromidite (VI) Tris(2,3-dibromopropyl) phosphite and bis(2-3-di-' bromopropyl) phosphorobromidite (VII) Tris(3-bromo-2-chloropropyl) phosphite and bis- (3-bro-mo-2-chloropropyl) phosphorochloridite (VIII) Tris(2-bromo-3-chloropropyl) phosphite and bis- (2-bromo-3-chloropropyl phosphorobromidite (IX) Tris(Z-chlorobutyl) phosphite and bis(2-ch1orobutyl) phosphorochloridite (X) Tris(Z-bromobutyl) phosphite and bis(2-bromobutyl) phosphorobromidite (XI) Tris(Z-chloro-l-methylpropyl) phosphite and bis(2- chloro-l-methylpropyl) phosphorochloridite (XII) Tris[(l-chloromethyDbutyl] phosphite and his- 1-chloromethyl)butyl] phosphorochloridite (XIII) Tris[(l-bromomethyl)-tert-amyl] phosphite and bis[(1-bromomethyl)-tertamyl] phosphorobromidite (XIV) Tris[(a-chloromethyl)benzyl] phosphite and bis (a-chloromethyl benzyl] phosphorochloridite (XV) Tris(2-chloro-2-phenylethyl) phosphite and bis(2- chloro-Z-phenylethyl) phosphorochloridite (XVI) Tris(2-bromo-2-methyl-2-phenylethyl) phosphite and bis(2-bromo-2-methyl-2-phenylethyl) phosphorobromidite (XVII) Tris(2-chloro-2-butenyl) phosphite and bis(2- chloro-3-butenyl) phosphorochloridite (XVIII) Tris(2-chloro-2-ethylhexyl) phosphite and bis- (2-chloro-2-ethylhexyl) phosphorochloridite (XIX) Tris(3-methoxy-2-chloropropyl) phosphite and bis(3-methoxy-2-chloropropyl) phosphorochloridite (XX) Tris(3-phenoxy-2-bromopropyl) phosphite and bis(3-phenoxy-2-bromopropyl) phosphorobromidite (XXI) Tris(3-iodo-2-chloropropyl) phosphite and bis(3- iodo-Z-chloropropyl) phosphorochloridite Since reaction of the oxirane compound with the phosphorus trihalide proceeds through opening of the oxirane ring, there may be present in the above mixtures minor amounts of isomeric phosphite and isomeric phosphorohalidite, e.g., while in the reaction of phosphorus trichlo ride and propylene oxide the oxirane ring opens with preferential formation of tris(2-chloropropyl) phosphite and bis(Z-chloropropyl) phosphorochloridite there may also be formed small quantities of tris(1-methyl-2-chloroethyl) phosphite and bis(l-methyl-Z-chloroethyl) phos- 11 12 phorochloridite. The isomer content, if any, of the reacthe aldehyde is a fatty aldehyde, the products obtained tion mixture is of no consequence for the present purpose from a mixture of phosphorohalidite and phosphorus ester because the isomers also react with the carbonyl comobtained by reaction of, say, two moles of phosphorus pound to give phosphite-phosphonates. While the small trichloride with more than four, but less than five, moles quantity of isomeric phosphite-phosphonate present in the of propylene oxide have the formula I i 'l n (CH$CHC1OH20)1P-OCHPO CHP(OOH2OHCICH9)2 L all: h J all:

CHzCHClCHa l1 final reaction product may be considered to constitute an in which all; denotes an alkyl radical of from 1 to 17 impurity, it is not detrimental in practical application, carbon atoms, and n is a number of from 1 to 10. When for the isomers are so closely related that they possess the same reaction product of propylene oxide and phossubstantially the same utility. Thus, the content of, say, phorus trichloride is treated with an aromatic aldehyde a small quantity of the bis(l-methyl-Z-chloroethyl) phosthe products have the formula F ll 1 11 (CHiCHClOHzO)sP-OOHPOCHP(OCHzOHClCHa):

l L aryl (I) J aryl CH2CHC1CH3 n phite of bis(1-methyl-2-chloroethyl) (l-hydroxyethyl) in which aryl denotes an aromatic hydrocarbon radical phosphonate in the bis(2-chloropropy1) phosphite of and n is a number of from 1 to 10.

bis(2-chloropropyl) (l-hydroxyethyl) phosphonate, which Reaction of a molar equivalent of the trivalent phosmay be present in the reaction product of acetaldehyde Phorus halogen Compound, a molar equivalent of the and the mixture of phosphite and phosphorochloridite aldehyde and less than a molar equivalent of the trivalent obtained from two moles of phosphorus trichloride and phosphorus ester takes place readily by contacting the ore than four but less than five moles of propylene three reactants at ordinary or moderately decreased or oxide, generally does not limit the utility of the latter. increased t mperatures and allowing the resulting re- However, if desired, the isomeric impurity may be sepaaction mtXture to stand until formation of the P rated by generally known isolating procedures, i.e., chro- Phosphorus oompourld- Thus, the Phosphorus halogen matography, crystallization, t compound may be mixed with the phosphorus ester in the Reaction of the phosphorus trichloride or phosphorus pp p ratio or a mixture thereof y be P p tribromide with the oxirane compounds takes place readfrom 3 Phosphorus trihahde and arr oXtraue compound ily, generally by simply mixing the phosphorus halide as disclosed above, and the aldehyde y be added to with the oxirane compound in the appropriate ratio. Dethe resulting miXtureif desired, the aldehyde and pending on the nature of the individual reactants, heatthe Phosphorus ester y first be mixed and the P i may or may not b required, Use f Catalytic phorus halogen compound added thereto. Because the amounts of an idi agent, 6%, h d hl id or reaction may be exothermic, gradual contact of the recompound which gives ff hydrogen chloride under actants is usually recommended in order to obtain smooth the reaction conditions, e.g., ethylene chlorohydrin, is adreaotioh- However, as Will be pp to those skilled vantageous. Usually the reaction is exothermic, whereby in the art, the cxothermal nature of the reaction becomes cooling in order to maintain smooth reaction is advanless of a factor as the molecular Weight o the reilotahts, tageous. It is recommended that in such exothermic reand Particularly of the phosphorus-sontaihlna actions the temperature he not allowed to rise above, actants, is increased. Also, when the aldehyde 15 either Say, f 0 C to 0 C An inert diluent may or may a higher alkanecarboxaldehyde or an aralkyl or alkaryl not be employed. When no diluent is used and there aldehyde, s h is generally not rapid as It is Wlth has been employed two moles f the phosphorus halide the lower aliphatic aldehydes or with benzaldehyde. It i more than f but less than fi moles f the is thus recommended that in each initial run, the three oxirane compound, the product consists of the haloreactants be mixed gradually at low temperatures and genated triorgano phosphite and a molar excess of the that external atmg be employed only when there aphalogenated diorgano Phosphorohalidite. Hence, no iso- Pears no p o s Increase In t p r t r as a 09nlating procedure is required before reaction with the alde- Sequence of the mlxmg- In most Instances, the reaction hyde for Preparation of the presently provided phosphite is mildly exothermic initially. Whether the reaction goes polyphosphohates Noting cessation of Change in rehab to completion without the use of extraneous heat 15 detertive index, or of heat evolution in the case of exothermic mlheo yt nature f the a tants- C0mplet1on of the reactions, or of change in viscosity of the reaction mass F h h eyerlt, earl e a y asoertalhefi y will suflice to determine When all of the initial reactants mg cessatfon change of o y, retraotlye lrldeX, have been consumed. The main consideration in preparthe quantlty ot byproduct hahdeg t lower aling the mixture of halogenated triorgano phosphite and 50 kaneclarboxaldehydes, Whroh aldehydes are g ne ally very halogenated diorgano phosphorohalidite is that the rereactrve, erfterhal hg is usually advantageous. When actants be employed in a ratio of 2 moles of the phosworklrrg Wlth such aehve aldehydes optimum it s phorus trihahde phr more than 4 but less than 5 moles comprise gradual addllllOI'l of the aldehyde to the m1xture of the oxirane compound of phosphite and phosphorus-halogen compound with ap- When formaldehyde is employed with a mixture of a plication of external cooling and thorough stirring.

phosphorohahdhe and phosphOrus ester obtained from Usually it suffices to maintain the reactio n temperature at, two moles of phosphorus trihalide and more than four Say, from to durlrlg addltrorl of the aideb l h fi moles f an lk l id h l hyde When all of the aldehyde has been added to said phosphorus compounds have the formula mixture and there is no longer any evidence of exothermic O reaction, completion of the reaction may be assured by I H I ll heating the reaction mixture to a temperature of from, say, 50 c. to 150 c. With the more sluggish alde- (h-haloalk n hydes, e.g., 2-phenylacetaldehyde or lauraldehyde, it may where haloalk denotes a haloalkyl radical of from 1 to be necessary to heat the reaction mixture moderately, say,..

12 carbon atoms and n is a number of at least 1. When to a temperature of about 50 C. before an exothermic 13 reaction is initiated. Employing naphthaldehyde as the aldehyde reactant and a high molecular weight phosphite and phosphorus-halogen compound, even higher temperatures may be required, e.g., temperatures of from 100 C. to 150 C. appear to give the best yields.

As stated above, formation of the desired product, i.e., the poly phosphorus compound, is accompanied by the formation of a by-product halide. Thus, the reaction of, say, dimethyl phosphorochloridite, acetaldehyde and triethyl phosphite gives ethyl chloride and methyl chloride as by-products:

(CHaOhP Ol-l-CH3CHO-l-(CHaCH2O)sP- The by-product halides are readily removed from the desired product by volatilization. However in many instances the by-product halides, particularly the halogenated alkanes are generally articles of commerce for which many applications exist. Thus, while many currently employed processes for the manufacture of organic compounds of phosphorus entail substantial waste of halogen in that by-products of little commercial importance are often formed, in the present instance, when starting from the phosphorus trihalideoxirane reaction products, all of the halogen constituent of the raw materials is converted to products of economic importance.

The process of the present invention is readily conducted in the absence of an inert diluent or catalyst. However, catalysts and diluents or solvents may be employed. The use of diluents may be particularly advantageous when working with the highly active aldehydes; such diluents may be, e.g., benzene, toluene, dioxane, methylene chloride, or hexane. When employing no diluent and using substantially the stoichiometric proportion of reactants, the reaction product may be used directly for a variety of industrial and agricultural purposes without purification, i.e., it consists essentially of the poly phosphorus compound dissolved in the halide which is produced as a by-product in the reaction.

The presently provided poly phosphorus compounds are stable, generally high-boiling, materials which range from viscid liquids to waxy or crystalline solids. They are characterized particularly by having a higher degree of hydrolytic stability than do the products obtained from equimolar quantities of each of the three reactants, i.e., the phosphorus halogen compound, the aldehyde and the phosphorus ester. This probably stems from the fact that the presently provided compounds have only one trivalent phosphorus ester group and a plurality of pentavalent phosphorus groups. While the utility of the whole class of the present compounds will range somewhat with the nature of each of the three reactants, the new poly phosphorus compounds are generally useful as lubricant and gasoline additives, as functional fluids in electrical and force-transmitting applications, as foam-suppressing and foam-regulating agents, as biological and agricultural toxicants, as rubber compounding chemicals, and as adjuvants for synthetic resins and plastics. They are particularly valuable as flame-proofing agents for cellulosic and carbonaceous combustible materials generally. Application of the present compounds, e.g., to cotton cloth by padding a solution or suspension of the compound, results in a smooth, flame-proofed cloth of improved hand, and of good color, resiliency and strength.

In applications relating to synthetic resins and plastics the present poly phosphorus esters are surprisingly useful in that not only do they impart flame-proofing and heatresistant characteristics thereto, but they also frequently demonstrate plasticizing properties. They are thus ad- I vantageously employed in the preparation of improved synthetics such as the phenolic, polyester, polyamide, and cellulose ester resins, in the vinyl polymers such as polyvinyl chloride, the polyvinyl acetals, polystyrene, polyethylene, vinyl chloride-vinyl acetate copolymers, olefinmaleic anhydride copolymers, polybutadiene and the copolymer elastomers such as butadiene-styrene or butadiene-acrylonitrile copolymers, etc. They are also very effectively used in the preparation of foamed resins, e.g., polystyrene foam or of polyester foams such as polyethylene terephthalate or the polyurethanes. Thus, use of the poly phosphorus compound with the required diisocyanate component and required hydroxy component in a quantity of, say, up to 40% of the mix gives foamed products which are not only flame-proofed but which also have been compatibly plasticized.

Those of the presently prepared poly phosphorus compounds which are gasoline-soluble are particularly useful as preignition additives for leaded gasolines. The invention thus provides an improved fuel for spark ignition internal combustion engines which consists essentially of gasoline, an organo lead anti-knock and the gasoline-soluble poly phosphorus compound, said compound being present in said fuel in a quantity suflicient to suppress preignition of the fuel.

Preignition is the ignition of the combustible mixture of air and fuel prior to firing by the spark plug. This occurs when deposits of readily glowing material build up in the combustion chamber. When the fuel is a. gasoline containing an organolead anti-knock together with a halohydrocrabon scavenger, such readily glowing deposits comprise carbon in a mixture with lead halides; the latter acting to reduce the normal ignition temperature of carbon. Since reduction of the ignition temperature tends to increase with increasing concentration of the organolead anti-knock, preignition is a problem which becomes particularly troublesome as use of high compression engines-becomes more prevalent. The deposits of carbon and lead salt retain sufficient heat from the previous firing cycle in enough quantity to permit them to glow, and if the glowing period (which depends on ease of ignition, and hence the lead content of the deposit) is long enough, the fuel is fired in the next cycle before it can be fired by the spark plug. The erratic firing which thus results is demonstrated by a wild ping or a dull, thudding knock. It is generally accompanied by increased detonation, spark-plug fouling, and reduction of exhaust valve life.

It has now been found that preignition and the various difiiculties consequent thereto can be substantially suppressed or entirely eliminated by incorporating the gasoline-soluble poly phosphorus compound into the leaded gasoline in a preignition-inhibiting quantity. Such a quantity, of course, will depend upon the content of organolead compound and halohydrocarbon scavenger in the fuel. Leaded gasolines usually contain an antiknocking quantity of an organolead compound such as tetraethyllead, tetramethyllead, dimethyldiethyllead, and tetraphenyllead and substantially the amount of hydrocarbon halide scavenger, say, ethylene dibromide, ethylene dichloride acetylene tetrabromide, or monoor polyhalopropane, butane, or pentane, or polyhaloalkyl benzene, which is calculated to react with the organolead compound to give a lead halide, e.g., lead bromide when the organolead compound is tetraethyllead and the halohydrocarbon is ethylene dibromide. The quantity of the present poly phosphorus compound which will suppress preignition of the leaded hydrocarbon fuel will depend upon the quantity of lead present in the fuel.

The invention is further illustrated by, but not limited to, the following examples:

Example 1 This example describes the production of a phosphite-diphosphonate by reaction of acetaldehyde with a mixture of phosphite and phosphorochloridite prepared from two moles of phosphorus trichloride and 4.67 moles of propylene oxide.

The mixture of phosphite and phosphorochloridite was prepared as follows: A 2-liter flask was charged with Example 3 550 g. (4.0 moles) of phosphorus trichloride and 4.1 g. (0.05 mole) of ethylene chlorohydrin. It was immersed in a Dry Ice bath and 539 g. (9.28 moles) of propylene chloropropyl) phosphite and lama-chloropropyl) phosphorochloridite by reaction of two moles of phosphorus 32 5 821 2 gf thereto durmg hour at a tempelature trichloride with 4.5 moles of propylene oxide and subse quent reaction of said mixture with acetaldehyde to obtain a condensate containing a plurality of phosphonate radicals and a single phosphite group.

A reaction vessel equipped with stirrer, thermometer, a protected water condenser and a protected dropping funnel was swept with nitrogen and then charged with the heat of reaction had subsided (about 0.2 hour after 550 moles) of phosphorus trichloride and adition of the aldehyde) the reaction mixture was warmed of ethylene chlorohydrin' The Vessel was cooled at 55-85" C. for 0.75 hour. A 5.0 g. analytical sample Dry Ice bath as 522 moles) of propylene made This example shows preparation of a mixture of tris(2- After removing a 6.0 g. sample of the resulting reaction mixture, the remaining reaction product, consisting of tris(2-chloropropyl) phosphite and bis(2-chloropropyl) phosphorochloridite in a one to two molar ratio, 10 was treated with 129 g. (2.94 moles) of acetaldehyde during 0.2 hour at a temperature of l530 C. When was removed and the remainder was concentrated to a s added during zoominutes at a temperature of pot temperature of 142 C./0.3 mm. to give 300.2 g. s y 15-20 T l l re l n mp:- (99% theoretical yield) of propylene di hl id i h ture was stirred for 0.5 hour to obtain a mixture consist- Dry Ice trap and as residue 901 g. (100% theoretical 3 essentially of Q- P PY phosphite and bis yield) of phosphite-diphosphonate, 11 1.4803, of the 20 (2-chloropropyl) phosphorochloridite in a one to three formula molar ratio.

a u r 1 (CHaCHC1CH1O)zP-OCH----ifOCH-P(OCH:CHC1CH:)1

i. CHaCHClCH2O in wherein n has an average value of 1. Cryoscopic molec- Nuclear magnetic resonance study of the mixture gave ular weight determination of the product in benzene gave a characteristic chemical shift of minus 168.5 p.p.m. for a value of 658 as compared to 680, the theoretical value. the phosphorochloridite and minus 141.8 p.p.m. for the Nuclear magnetic resonance spectra for phosphorus phosphite. showed characteristic chemical shifts at minus 141.6 To the mixture of phosphite and phosphorochloridite p.p.m. (relative to H PO for the trivalent phosphorus there was added, during 10 minutes, 145 g. (3.3 moles) and at minus 21.5 p.p.m. for the pentavalent phosphorus. of acetaldehyde. During addition of the aldehyde, the The product analyzed as follows: temperature of the reaction mixture was maintained at 1520 C. by cooling, and it was maintained at this tem- Founq 0816a for perature for an additional 0.5 hour after all of the alde- CWHHCISOQPfl hyde had been added. At the end of this period, no further heat of reaction was evidenced, and in order to deg 2% 2:2 termine whether all of the chloridite had reacted, the mix- Percent off I: 26.08 26.1 40 ture was warmed and another 5.0 g. portion of acetalde- P919911 P 13-68 hyde was added. A 1.0 C. temperature rise was noted; but the addition of another 5.0 g. of the aldehyde caused Example 2 no temperature change. The colorless reaction mixture This example Shows preparation of a phosphite di was then warmed at 85-90 C. for 0.5 hour to assure phosphonate by reaction of a phosphorochloridite and 4 Complete react1011- By-product P py dichloride was an aldehyde with a previously prepared phosphite of a removed y Placing the mixture under Vacuum and c011- hydroxyalkyl-phosphonate. centrating, with stirring, to a pot temperature of 125 The bis(2-chloropropyl) phosphite of bis(2-chloro- C./0.5 mm. There was thus obtain as residue 890.0 g. propyl) 1-hydroxyethylphosphonate was prepared by reof a polyphosphonate-phosphite of the formula I" E H u (CHzCHClCHgO)gP-OCH-P0CHP(OCH2CHC1OH2)2 onsofloionzol.

action of acetaldehyde with an equimolar mixture of wherein n has an average value of 2.

bis(2 chloropropyl) phosphorochloridite and tris(2- chloropropyl) phosphite. To 248 g. (0.5 mole) of this Example 4 compound there was first added 126.8 g. (0.5 mole) of This example is like Example 1 except that the phosbis(2-chloropropyl) phosphorochloridite and to the rephorus trichloride and the propylene oxide were emaction mixture there was introduced during a time of ployed in a 2:4.75 ratio.

0.2 hour, 26.4 g. (0.5 mole plus 20% excess) of acetalde- Propylene oxide (552 g., 9.5 moles) was added, during hyde while maintaining the temperature of the reaction 20 minutes, to a mixture consisting of 550 g. (4.0 moles) mixture at 25-35 C. by cooling. The whole was then of phosphorus trichloride and 2.75 g. of ethylene chlorowarmed to 80-90" C. for 0.3 hour and then concentrated hydrin while maintaining the temperature of the reaction to 142 C./0.2 mm. to give 58.4 g. of distillate in mixture at 10-20 C. (largely 1520 C.). A 6.0 g. the trap which formed a part of the reaction equipment sample was removed for analysis. To the remainder of (theory is 56.6 g. of by-product 1,2-dichloropropane plus the reaction mixture, which consisted essentially of a 4.4 g. excess acetaldehyde), and 340.9 g. (100% theoretimixture of tris(Z-chloropropyl) phosphite and bis(2- cal yield) of the phosphite-polyphosphonate, 11 1.4807, chloropropyl) phosphorochloridite, there was added 127 of the structure g. of acetaldehyde, during 5 minutes, while maintaining r E ll t r (CHaCHClCHzO)gP-OCH-lr-OCHP(OCHzCHClCHa):

L OHzCHOlCHzO ie wherein n has an average value of 1. This product was the temperature of the reaction mixture at 1820 C. by essentially identical to that prepared in Example 1. mild cooling. The colorless reaction mixture was then 18 chloride in the Dry Ice trap and as residue a polyphosphonate-phosphite of the formula l oloHzorndl. CH where n has an average value of 2.

where n is 1.

This mixture, which has an average atomic ratio of C H Cl O P analyzed as follows:

Found Calcd. for

C13H!6C13.506P2 Percent C 33. 77 33. 65 Percent H." 5. 83 5. 65 Percent Cl 26. 62 26. 75 Percent P 13. 33 13. 36

Example 5 This example is like Example 4 except that it was conducted on a large scale in the pilot plant.

The reaction mixture comprising the polyphosphonatephosphite analyzed as follows:

Found Calcd. for

C|3H2C13.5O5P2 Percent C 33. 56 33. 65 PercentH 5.81 5.65 Percent 01 26. 59 26. 75 Percent P 13. 39 13. 36

Hydrolytic stability of the present product was compared with the phosphite-phosphonate,

O H (CHzCHC1CH20)2P O CH]? (O CHzCHClCHah Example 6 This example describes reaction of two moles of phosphorus trichloride with 4.5 moles of ethylene oxide to obtain a mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite and subsequent reaction of said mixture with acetaldehyde to obtain a polyphosphonate-phosphite.

To 1100 g. (8.0 moles) of phosphorus trichloride and 8.3 g. of ethylene chlorohydrin there was added 793 g. (18.0 moles) of ethylene oxide during 0.75 hour while maintaining the temperature of the reaction mixture at 10-20 C. (largely 10-15 C.). A 6.0 g. sample was removed for analysis and to the remaining mixture of tris (Z-chloroethyl) phosphite and bis(2-chloroethyl) phosphoro-chloridite there was added 290 g. (6.6 moles, 10% excess) of acetaldehyde during 0.3 hour while maintaining the temperature of the reaction mixture at 25-30 C. by cooling. When all of the acetaldehyde had been added, cooling was discontinued and the temperature of the reaction mixture increased spontaneously to 52 C. The mixture was then warmed at 8590 C. for 0.5 hour, cooled to 30 C. and then concentrated to a pot temperature of 110 C./1 mm. to give 553.5 g. of ethylene di- Testing of the hydrolytic stability of the presently prepared polyphosphonate-phosphite employing the procedure described in Example 5 gave a value of 0.966 milliequivalent of NaOH/ g. sample as compared to 1.852, the value obtained by similar testing of the phosphitephosphonate of the formula 0 II (C1CHiCH20)zPO (IJHP (O CHzCHzCl):

CH3 Example 7 This example shows the preparation of a phosphitepolyphosphonate from two moles of phophorus trichloride and 4.5 moles of ethylene oxide and acetaldehyde as in Example 6 but without removal of by-product ethylene dichloride.

A mixture of tris(Z-chloroethyl) phosphite and bis(2- chloroethyl) phosphorochloridite was prepared by adding 793 g. (18.0 moles) of ethylene oxide to a mixture consisting of 1100 g. (8.0 moles) of phosphorus trichloride and 8.2 g. of ethylene chlorohydrin with cooling at 10- 20 C. (largely l0-15 C.) during 1.25 hours.

After removing a 6.0 g. sample from the reaction product, the remainder, which consisted of tris(2-chloroethyl) phosphite and of bis(Z-chloroethyl) phosphorochloridite in a 1:3 ratio, was treated with 290 g. (6.6 moles, 10% excess) of acetaldehyde at 2030 C. during 0.2 hour. Cooling was applied to maintain this temperature during addition of the acetaldehyde and for another 0.7 hour after the aldehyde had been added. The reaction temperature was finally allowed to increase spontaneously to 41 C. The resulting reaction mixture consisted of an ethylene dichloride solution of the polyphosphonate-phosphite of the formula O(?HP(OOH2CHzCl)2 r r t (CHzClCHzOhP-OCH-P oorrzcmoii. CH:

where n has an average value of 2. Nuclear magnetic resonance measurements on this product showed a characteristic chemical shift of -142 p.p.m. (relative to H PO for the trivalent phosphorus and of 22 p.p.m. for the pentavalent phosphorus.

Example 8 This example shows preparation of a polyphosphonatephosphite by reaction of 1.75 moles of acetaldehyde with a mixture of tris(Z-chloropropyl) phosphite and bis(2- chloropropyl) phosphorochloridite prepared by reacting two moles of phosphorus trichloridite with 4.25 moles of propylene oxide.

To a mixture consisting of 550 g. (4.0 moles) of phosphorus trichloride and 2.75 g. of ethylenechlorohydrin there was added, with cooling during 0.4hour, 493 g. (8.50 moles) of propylene oxide. About the first twothirds of the oxide was added at a temperature of 5-15 C. and the last one-third at 0-5 C. A 9.0 g. sample of the resulting reaction mixture was removed for analysis and the residual mixture, consisting essentially of tris(2- chloropropyl) phosphite and bis(Z-chloropropyl) phosphorochloridite in a 1:7 molar ratio, was treated with Found Calcd. for

Percent C 33. 35 33.0 Percent H 5. 53 5. 54 Percent 01 22. 59 22.1 Percent P 15.06 15. 5

Testing of the hydrolytic stability of the presently prepared polyphosphonate-phosphite as described in Example 5 gave a value of 0.392 milliequivalent of NaOH/ g. sample.

Example 9 This example shows reaction of two moles of phosphorus trichloride with slightly more than 4 moles of propylene oxide to obtain a mixture consisting essentially of a small amount of tris(2-chloropropyl) phosphite and a major portion of bis(Z-chloropropyl) phosphorochloridite and reaction of said mixture with acetaldehyde.

Propylene oxide (233 g., 4.02 moles) was added during 0.2 hour to a mixture consisting of 275 g. (2.00 moles) of phosphorus trichloride and 1.5 g. of ethylene chlorohydrin while cooling to maintain the temperature of the reaction mixture at 515 C. during about the first one-third of the addition of the oxide and at minus 50 C. during the remainder of the addition. The resulting mixture of tris (2-chloropropyl) phosphite and bis(Z-chloropropyl) phosphorochloridite was allowed to warm spontaneously to 20 C., a 6.5 g. sample of the mixture was removed for analysis and stirring of the whole was continued at room temperature for one hour. At the end of this time, 101 g. (2.3 moles, 15 excess) of acetaldehyde was added to the mixture during 0.2 hour with cooling to keep the temperature at 20 25 C. It was then allowed to stand for 0.3 hour while cooling to maintain the temperature at 20-30 C. At this point there was no further evidence of exothermal reaction and the reaction mixture was warmed at 8090 C. for 0.5 hour. A 6.0 g. sample was removed for analysis and the remainder was concentrated to a pot temperature of 100 C./2.0 mm. to give as residue 443.5 g. of colorless, viscous polyphosphonatephosphite.

Example 10 This example shows preparation of a polyphosphonatephosphite by reacting two moles of PCI;, with 4.75 moles of ethylene oxide to obtain a mixture of tris(Z-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite and condensation of said mixture with 1.25 moles of acetaldehyde.

To a mixture consisting of 550 g. (4.0 moles) of phosphorus trichloride and 2.75 g. of ethylene chlorohydrin there was added 418 g. (95 moles) of ethylene oxide during 0.75 hour while cooling the reaction mixture at 12- 20 C. with a Dry Ice bath. The whole was then stirred for one hour and a 6.0 g. sample removed for nuclear This mixture of tris(Z-chloroethyl) phosphite and bis(2- chloroethyl) phosphorochloridite was cooled at 2530 C. while 127 g. (2.89 moles, 15 excess) of acetaldehyde was added during 0.3 hour. The resulting reaction mixture was maintained at 25-30 C. for another 0.5 hour and then allowed to stand without cooling, whereby a maximum temperature of 59 C. developed spontaneously. When there appeared to be no further exothermic reaction, the reaction mixture was warmed at -90 C. for one hour and finally concentrated to a pot temperature of C./0.1 mm. to give 239.5 g. of by-product ethylene chloride and as residue 843.5 g. of the colorless liquid reaction mixture, n 1.4910, of which two-thirds in moles consisted of a polyphosphonate-phosphite of the formula This example describes the preparation of a polyphosphonate-phosphite by reacting two moles of phosphorus trichloride with 4.75 moles of propylene oxide to obtain a mixture of tris(Z-ehloropropyl) phosphite and bis(2- chloropropyl) phosphorochloridite and subsequent reaction of said mixture with formaldehyde.

To a cooled mixture consisting of 550 g. "(4.0 moles) of phosphorus trichloride and 2.75 g. of ethylene chlorohydrin there was added, during 0.4 hour, 552 g. (9.5 moles) of propylene. oxide while maintaining the temperature of the reaction mixture at 12-20 'C. A 6 g. sample of the reaction mixture was removed. The remaining mixture of tris(2-chloropropyl) phosphite and bis-(2-chloropropyl) phosphorochloridite was warmed to 40 C. and g. of formaldehyde was distilled into said mixture during 1.25 hours while maintaining the tem perature of the reaction mixture at 45-65 C. by occasional cooling. The residue was then distilled to a pot temperature of 150 C., placed under vacuum and concentrated to a pot temperature of C./0.05 mm. to give as residue 918 g. of the colorless, liquid reaction mixture of which two-thirds in moles consisted of a polyphosphonate-phosphite of the formula O H u OCH1POCH3P (O CHzCHClCHs):

Example 12 CHaCHClCHz |n LCHaCHClCHz where n is 1.

where n has an average value of 10.

Example 13 This example shows preparation of a phosphite-diphosphonate from triethyl phosphite and diethyl phosphoromagnetic resonance study, whereby there were observed a 75 chloridite.

21 22 To a mixture consisting of 113 g. (0.72 mole) of dispontaneously to 40 C. during addition of the epichloroethyl phosphorochloridite and 60 g. (0.36 mole) of trihydrin. The reaction mixture was then maintained at ethyl phosphite there was added 38 g. (0.86 mole) of acet- 50-60 C. with mild cooling until there was no further aldehyde during 0.3 hour while maintaining the temperaheat of reaction (1.25 hour), and subsequently warmed ture of the reaction mixture at 20-25 C. The temperafor 0.5 hour at 5560 C. to assure complete reaction. ture was maintained at 25-30 C. for another 0.2 hour After removing a 10.0 g. sample of the reaction mixture at which time there was no further evidence of exotherfor analysis, the remaining mixture of tris(2-bromo-3- mal heat. It was then warmed at 50-75 C. for one hour chloropropyl) phosphite and bis(2brorno3-chloroproto assure complete reaction and concentrated to 100 C./ pyl) phosphorobromidite was cooled to C. and there 0.05 mm. to give as residue 145 g. of the phosphite-poly- 10 was added thereto 57 g. (1.29 moles) of acetaldehyde phosphonate, 11 1.4522, of the formula during 0.1 hour while maintaining the temperature at CH 0 CH3 0 2030 C. by cooling. When all of the aldehyde had (CHSCHzOhP J CHZCHM been added, the mixture was kept at -55 C. for 0.5 CHECK) n hour by cooling, and when there was no further evidence 15 of exothermal reaction, an additional 10 g. of acetaldehyde was added. A temperature rise of 1 C. was noted. Example 14 The whole was then warmed to C. and concentrated This example describes the preparation of a polyphos- 2 (310-05 o glve by-product 2-bromo-l,3- phonate-phosphite by reacting two moles of phosphorus dlchlol'opropzme the Dry Ice trap Whlch formed P where n has an average value of one.

trichloride with 4.9 moles of epichlorohydrin to obtain a 20 of the equipment and as residue 850 of p p mixture of phosphite and phosphorochloridite and react- .P P P of which tW0-thifd$ in moles ing said mixture withacetaldehyde. sisted of the polyphosphonate of the formula r r t r t (CHZOICHBI'CHZO)2P OCHli-OCH--P(OCH2CHBrOHzCl)z LCHgClCHBrOHzOJn To a mixture consisting of 413 g. (3.0 moles) of phos- Evaluation of the hydrolytic stability of the presently phorus trichloride and 4.1 g. of ethylene chlorohydrin prepared polyphosphonate-phosphite mixture using the there was added, during 0.4 hour, 680 g. (7.35 moles) of method described in Example 5 gave a value of 0.304 epichlorohydrin. Because at the beginning of the addimilliequivalent of NaOH/g. sample.

tion of the epichlorohydrin only mild heat of reaction was noted, the reaction mixture was warmed to 60 C. At that point the reaction was sufliciently vigorous that s e ple describes the preparation of a polyphosthe temperature remained at 6065 C. without external p onate-pho phite by reaction of tWo moles of phosphoheating during addition of the remainder of the epichloror trichloride With 1110168 f 1,2-ep0Xy-3-isopropoXyhydrin. The temperature was then allowed to increase propane to obtain a mixture of phosphite and phosphoroto C. and it was maintained at 8590 C. by modchloridite and reaction of said mixture with undecaldeerate cooling for 0.75 hour. After standing overnight, a hyde.

6.0 g. sample of the reaction mixture was removed for 40 To a mixture consisting of 49.2 g. (0.358 mole) of analysis and to the remaining mixture of tris(2,3-dichlophosphorus trichloride, 0.5 g. of ethylene chlorohydrin and ropropyl) phosphite and bis(2,3-dichloropropyl) phosml. of methylene dichloride there was gradually addphorochloridite there was added, during 0.3 hour, 83.5 ed, during 0.2 hour, 100 g. (0.860 moles) of 1,2-epoxy- Example 16 g. (1.9 moles) of acetaldehyde while maintaining the 3-isopropoxypropane while cooling the reaction mixture temperature of the reaction mixture at 20-30 C. by coolto maintain the temperature thereof at 20-30 C. The ing. It was then warmed to reflux C.), then dis- 45 whole was then maintained at 2530 C. for 0.2 hour and tilled to a pot temperature of C. and finally consubsequently warmed at reflux for 0.3 hour. After recentrated to 150 C./2.0 mm. to give 987 g. of a colormoving a 5.0 g. sample of the reaction product for analless, liquid residue, of which two-thirds in moles conysis, the remaining mixture of tris(2-chloro-3-isopropoxysisted of a polyphosphonate-phosphite of the formula propyl) phosphite and bis(2-chloro-3-isopropoxypropyl) E til t t (CH:ClCHClCH20):P-OCHP OCHP(OCH2CHC1OH4C1)1 LCHzClCHClCHz I where n is 1. phosphorochloridite was treated with 36.6 g. (0.215 Example 15 mole) of n-undecanal during about 5 minutes at 35-47 This example describes the preparation of a polyphos C. The resultlng reaction mixture was warmed at rephonate phosphite by the reaction of two moles of phos flux for 1.0 hour, concentrated at water-pump pressure to phorus tribromide with 4.9 moles of epichlorohydrin to 60 and finally t0 to g as residue give a mixture of phosphite and phosphorobromidite and 159-8 gof a P P "P P P of Which reaction of the resulting mixture with acetaldehyde. one-half in moles consisted of the polyphosphonate-phos- To a mixture consisting of 507.0 g. (1.87 moles) of phite of the formula ll OOHP OCH-P(OCH2CHCICH2O CHMez):

CHCI

MezCHO CH: 11

(Me CHO CHzCHC1CH20)RP phosphorus tribromide and 2.5 g. of ethylene chlorohydrin there was added 415 g. 4.49 moles) of epichlorowhere the methylrafhcal f f 1s hydrin during ()3 houn There was only mild heat f Evaluation of hydrolytlc stability of the presently proreaction, so the temperature was allowed to increase 7 vided polyphosphonate-phosphite employing the proce- 23 24 dure described in Example gave a value of 0.539 milliupon an exothermal reaction occurred and cooling was equivalent of NaOH/g. sample. required to maintain the temperautre of the reaction mixture at 85-95 C. for 0.5 hour. It was finally warmed at 100-105 C. for 0.5 hour and concentrated to 100 T1115 eXamP1e de51'1be$ the Preparation of a P l P 5 C./2 mm. to give as residue a phosphite-phosphonate phohate-phosphlte by the reaction of two moles of P product, of which 50% in moles consisted of a phosphorus trichloride with 4.8 moles of butadiene monoxide h h hi f th fo mula to obtain a mixture of phosphite and phosphorochloridite Example 17 0 OOHzOHzOl o and reaction of said mixture with propionaldehyde. H

To a cooled (l5 C.) mixture consisting of 274.7 g. 10 (O1CH1CH2OhP-OCHP OCHHOCHCHCDZ (2 moles) of phosphorus trichloride and 2.7 g. of ethyl- 0 0 ene chlorohydrin there was added, during 0.3 hour, 336 g. (4.8 moles) of butadiene monoxide. A 5.5 g. sample II II II II of the reaction mixture was removed and to the remain- (DH-CH CH CH ing mixture of tris(2-chloro-3-butenyl) phosphite and bis- Where 15 (2-chloro-3-butenyl) phosphorochloridite there was add- Example ed 101.5 g. (1.75 moles) of propionaldehyde during 0.3 This example describes the preparation of a polyphoshour at a temperature of 20-35 C. The whole was phonate-phosphite by reaction of two moles of phosthen warmed to 70 C. and concentrated to 102 C./4.0 phorus trichloride and 4.8 moles of ethylene oxide and mm. to give as residue 562.5 g. of phosphite-phosphonate 20 subsequent reaction of the resulting mixture of phosphite product, of which one-half in moles consisted of the polyand phosphorochloridite with fl-methylmercaptopropionphosphonate-phosphite of the formula aldehyde.

H i u (CHg=CHGHOlCH:O)qPOCHPOCH--P(OOH:CHC1CH=CH:)1

LCHg=CHOHClOH2 iLL Where Et is the ethyl radical and n i To 244 g. of the mixture of tris(Z-chloroethyl) phos- Example 18 phite and bis(2-chloroethyl) phosphorochloridite pred'E 118th ddd,d 0.2,

This example describes Preparation of a polyphosphoi m fi lz of aiiritifsiiierez w i xn314513 212 322838585334t fiafififlteifiii pififiiiigif W gg jg g f3: a a g g t t pane and reaction of the resulting mixture of phosphite :oncentrated to 3;: j8f Z g g- 3 of g pgg r i g g ggg g g g gp g gfig of hos ethylene dichloride in the Dry Iee trap which formed'a h hl id 1 5 g f l m h d P (5 part of the reaction equlpment and asresidue aphosplnte- P orus or o e yene 0 0m Y rm an phosphonate product, of which 50% in moles consisted 200 ml. of methylene dichloride there was added, during f th 1 h 0.25 hour, 360 g. (2.4 moles) of 1,2-epoxy-3-phenoxypro- 0 6 p0 yp Osphonate phosp l e of the formula pane. The temperature of the reaction mixture increased i spontaneously to reflux (pot temperature of 58 C.) dur- 40 (ClCHzCHz )zPO CHP-O CHP(O CH2CH:C1)2 ing the addition and subsequent heat of reaction kept E OHQOHZSCHB the mixture at reflux for 0.5 hour. It was then warmed l I with a heating mantle at reflux for one hour to assure I i I complete reaction. To the resulting reaction mixture, 5 CHaCl comprising tris(2-chloro-3-phenoxypropyl) phosphite and D bis(2-chloro-3-phenoxypropyl) phosphorochloridite, there where n is 1 was added 71.8 g. (1.24 moles) of propionaldehyde dur- Exam 21 ing 0.2 hour while maintaining the temperature of the p reaction mixture at 35-50" C. by cooling. The whole This example describes preparation of polyphosphowas then warmed at reflux for 0.5 hour and concentrated mate-phosphite by the reaction of two moles of phosphorus to 115 C./2 mm. to give as residue 558 g. of a mixture trichloride with 4.8 moles of ethylene oxide to obtain a of by-product 2,3-dichloropropyl phenyl ether and a phosmixture of phosphite-phosphorochloridite with subsephite-phosphonate product, of which 50% in moles conquent reaction with acrolein. sisted of the polyphosphonate-phospite of the formula T0 486.5 g. of the mixture of tris(Z-chloroethyl) phosl' 1 Ii I 1 n (CQHgOCHaCHClCHzO)gP---OCH-1r--OOHP(OCH:CHO1CH2OCH)| CaHsOCHzCHClCHz n where Et is the ethyl radical and n is 1. phite and bis(2-ch1oroethyl) phosphorochloridite pre- Example 19 pared in Example 18 there was added 70.6 g. of acrolein This example describes preparation of a polyphosphodunngc one hour Yvhlle mamtalmng the temperature at nate-phosphite by reaction of two moles of phosphorus 1040 y 00011118- e Whole w s then warmed to trichloride with 4.8 moles of ethylene oxide to obtain a 05 and concentrated (10 to give 437 mixture of phosphite and phosphorochloridite and reaction gof p OSphite-phosphonate product of which 50% in of said mixture with furfural. moles consisted of the polyphosphoIrate-phosphite of the To a mixture consisting of 1100 g. (8.0 moles) of formula phosphorus trichloride and 8.2 g. of ethylene chlorohydrin there was introduced, during 1.2 hours, 845 g. (19.2 CH=CH2 moles) of ethylene oxide at 10-20 C. To one-half g CHzGH,

(973 g.) of the resulting mixture of tris(2-chloroethyl) phosphite and bis(2-chloroethyl) phosphorochloridite (CICHCHZmP L J ocHPwcmoHcl) there was added 231 g. (2.4 moles) of furfural during 0031011101 n 0 0.2 hour. The whole was then warmed to 90 C. wherewhere n is 1.

Example 22 formed a part of the reaction equipment and agfiresidu; 946.5 of a phosphonite-phosphinate product, n 1.547 ThlS exam le describes the reparatlon o f a polyphos- P phonate-phos phite wherein acr olein is employed as the of whlch a lilolesufonslsted of the poly Phosphorus aldehyde and the molar ratio of phosphorus trichloride compoun o t e a and propylene oxide is 2:4.9. 5 OBHE CH3 0 CH3 0 OGHB To a cooled mixture consisting of 1100 g. (8.0 moles) P F J L l OH P of phosphorus trichloride and 8.2 'g. of ethylene chloro- T- l hydrin there was added, during 0.8 hour, 1 136 g. of (19.6 GHaGHClCHzO CaHa 00112011010115 moles) of 1 r0 ylene oxide while maintaining the ternperature of th reaction mixture at 20 C. (largely 10 Where 10-15 C.). A 6.5 g. sample of the reaction mixture Example 25 was removed and to the remaining mixture of tris(2- chloropropyl) phosphite and bis(2-ch1oropropy1) 1 Thls example descrlbes preparation of a phosphrtephorochloridite there was added during 0.25 hour, 246.6 g. diphosphonate having di ssimilaf alcohol residues- (4.4 moles) of acrolein while maintaining the tempera- To a S01115011 conslstlng 0f g. 111016) of ture of the reaction mixture at 24-30 C. by cooling. bi$(2 p 'py Phosphorochloridite and 8- When cooling was discontinued the temperature of the molelof ll'iethyl Phosphite in 30 of y reaction mixture increased spontaneously to 41 C. It fine Chloride th r as added during 0.1 hour 3.8 g. was then heated to 103 C. and maintained at 85-103 mole) of Propionaldehyde While m tai ng the C. for 0.75 hour. Concentration of the resulting reaction temperature of the reaction mixture at 2030 C. by mixture to 120 C./'1 mm. gave 455.5 g. of by-product Cooling. When heat of reaction was no long r evident propylene dichloride which collected in the Dry Ice trap hour after all of the aldehyde had been forming part of the equipment and as residue a phosadded), the mixture was warmed at reflux for 0.5 hour,

phonate-phosphite product, of which two-ninths in moles 25 distilled to a pot temperature of 70 C., and then conconsisted of the polyphosphonate of the formula centrated to 107 C./0.2 mm. There was thus obtained CH=CH2 l l t l H (CH= CHClQH1O)nPOCHP OCHP(OCHCHC1CH3)2 v L OCHZCHCIOHS-lh OH=CH1 where n is 1. as residue the phosphite polyphosphosphonate, n

Example 23 1.4696, of the formula: This example discloses the use of an aldehyde ester in CHacHr H the preparation of a phosphite-polyphosphoriate. (CH3OHC1OH20)2P -|:OCH--PTO?HP (OCHzCHa):

To 72 g. of a mixture of tris(2-chloroethy phosphite v 7 and bis(2-chloroethyl) phosphorochloridite prepared by CHJCHCICH: (JHzCHa the reaction of two moles of phosphorus trichloride with where n h a average value of 1, 4.8 moles of ethylene oxide there was added with icecooling in one portion, 19.5 g. (0.15 mole) of ethyl Example 26 3-formylpropionate. The temperature of the reaction l mixture increased spontaneously from 28 C. to 52 C. This example ShOWS f ff a P Q P -P YP When there was no further evidence of exothermal rep Product as Prelgmtlon additive for leaded action, the mixture was warmed to 83 C. and then 0011- gasollllecentrated to a pot temperature of 122 C./0.6 mm. to Since it has been established that there is a close give 13.4 g. of by-product ethylene dichloride in the Dry r lationship between the quantity of a material required to Ice trap and 78.5 -g. of a phosphite-phosphonate product, uppress glowing and the effectiveness of the same maten 1.4863, of which in moles consisted of a phosrial for reducing preignition of a leaded fuel in gasoline phite-polyphosphonaite of the formula 50 engines, testing of the presently prepared polyphos- CHsCHzOaOCHaCHz O O (ClCHaCH20)2P -OCH% OCHl (OCHzCH:CI)2 L 0101 1 01110 OHQCHQCOiCHflGHS where n is 1. phonate-phosphites was conducted by a glow test method Example 24 wherein the following procedure was employed: I Test blends were prepared by blending (1) 5 ml. of a To a mixture consisting of 716 g. (4.0 moles) of phenylo phosphonous dichloride and 7.1 g. of ethylene chloroz g of thlgll'bolhng hydro; hydrin there was added 336 g. (5.8 moles) of propylene 6o f g lz afppmmmate l g oxide during 0.25 hour while maintaining the temperaea age on e quan y. a conlmelma tetraet y ture of the reaction mixture at 0-5 C. by means of Dry i'gi g gli ii g g addlmve (heregnafiter g f f Ice cooling. The reaction was rapid, very exothermic, as W 10 een.mc9rpor.ate erem an and was complete by the time all the propylene oxide of l SAE grade ll on Wlth (2) graduated had been added A 7 0 g samplg of the reaction prod precisely weighed quantities of the poly phosphorus comuct was removea for mal'ysis and to the remaining pound to betested, said quantities being in the range of action product, consisting of 2-chloropropyl phenylphosfi the i i' of a Present Two phonochloridite and bis(2-chloropropyl) phenylphospho- 0 t e est en en roPpe at a consiam rate nite, there was added, during 0.2 hour, 197 g. (2.42 moles) mL/ 15 g z duimg mmute. of acet a1 dehy de Moderate cooling was employed to r10 onto a reagent gra e eco OIlZlIlg car on contained keep the temperature below 320 during additiofi of the In a crucible malntained 1n a furnace at a temperature aldehyde and for about 0.25 hour after all of the aldehyde 9 was hlgh enough to e the bottom of the had been added. The colorless, viscous reaction mixcrumble at Y 118mg test blends C ntamture was then warmed at 55-65 C. for one hour and then ing progressively lower quantities of the test compound, concentrated to 90 C./1 mm. to give 207.5 g. of the there was determined the minimum concentration of the by-product propylene dichloride in the Dry Ice trap which test compound at which no glowing of the carbon was evidenced either during the dropping period or after all haloalkyl, alkoxyalkyl, aryloxyalkyl, haloalkenyl, alof the test sample had been added. Under these condikoxyalkyl, aryloxyalkyl, alkoxyhaloalkyl and phenoxytions, a control sample, i.e., one which contained all haloalkyl radicals of from 1 to 12 carbon atoms, R is of the constituents of the test blend execpt the poly selected from the class consisting of OR monocyclic phosphorus compound caused the carbon to glow 5 and aromatic hydrocarbon radicals of from- 6 to 12 carthroughout addition thereof and after addition had been bon atoms, Z is selected from the class consisting of completed. On the other hand, no glowing was observed hydrogen and alkyl, alkenyl, aryl, alkylthioalkyl, and when there was present in the test blend 0.0408 g./5 ml. carboalkoxyalkyl radicals of from 1 to 17 carbon atoms of said fuel of the poly phosphorus compound prepared and the furyl radical, and n is at least 1.

by reacting two moles of phosphorus trichloride with 2. A compound of the formula 4.75 moles of propylene oxide to obtain a mixture of Y Y I- O O Y Y bis(2-chloropropyl) phosphorochloridite and less than I I II I I (ClCHCHO)zP--O OCHP(OCHCHC1);

a molar equivalent of tris(2-ehloropropyl) phosphite and a reacting said mixture with a molar equivalent of acetal- Z OCHOHCI z dehyde, i.e., the compound of Example 4. u

Instead of the bis(2 chloropropyl) phosphorochloridite tris(2-chloropropyl) phosphite-acetaldehyd wherein Y is selected from the class cons1st1ng of hydrotion product Ishown above, (them may be used for the gen, alkyl, haloalkyl and alkenyl radicals of from 1 to purpose of eifeetively inhibiting preignition of leaded 6 f atoms, and lk xyalkyl and phenoxyalkyl f l any f the gasoline soluble compounds prepared 20 radicals of from 2 to 7 carbon atoms, Z 1s selected from according to the present process. While, as will be the c1a5 conslsmng of hydrogen and y y aryl, obvious to those skilled in the art, the compound to be alkylthloalkyl 811d carboxyalkyl radicals of from 1 t0 7 useful must be present in the gasoline in soluble form, it on atom and the furyl radical, and n is at least 1. will also be realized that since the additive is employed 3. A compound of the formula l Lalk (l) j alk CHzCHClCHs n in only very low concentrations, gasoline solubility at in which 31k denotes an alkyl radical of from 1 to 17 the useful concentrations is Possessed the great atoms and n is at least 1.

ponderance of the presently prepared compounds. Whether the poly phosphorus compound is soluble in A compound of the formula CH3 0 CH: O l I II II OHP-OCHP (O 0112011010113): CHQCHCICHZ .In

the gasoline at the useful concentration can be readily wherein n is at least 1. ascertained by rountine experimentation. 40 5. A compound of the formula Inasmuch as the crude reaction mixture obtained by CH3 0 O I II II the present process comprises an allphatlc halohydro CH2 O1 CH2 O OCHHOOHZCHZCDZ (CH3GHOIOH20)ZP carbon as by-product, the latter obviously can serve con- L J) J E viently as the lead scavenger in leaded gasoline fuels 112011201 11 H1 containing the presently prepared poly phosphorus comwherein n is at least 1. pounds. 6. A compound of the formula Leaded gasolines containing the presently prepared CH3 0 CH! 0 compounds are compatible with other additives custom- I I] (OHaCH2O)aPOCH OCH-P(I)CH;CH:)2

arily used in the art, e.g., rust-inhibitors, stabilizers or antioxidants, dyes, etc. The polyphosphorus compounds LOHQCHg L of this invention may be employed in diiferent proportions than specifically shown and with such other additives and adjuvants.

The presently provided process is particularly useful CH3 0 CH3 0 because of the broad variation of products that can be (GHzOHClCHOhP g obtained. Not only can the reactants be varied to give L C innumerable products, but the ratio of reactants can be HCICHZO changed to even further multiply the products obtainable. wherein n is a number of at least 1. 0f considerable usefulness is the variation in properties, such as change of viscosity, volatility, fire resistance, A P' of the hydrolytic stability, solubility, and polarity (that can be whfire E1 8 the ethyl radical, C H denotes the phenyl made by change of reactant ratios. radlcal: and n 15 at least Wherein n is at least 1.

7. A compound of the formula What I claim 9. The method of preparing the compounds defined in 1. A com ound f the fonnula 0 claim 1 which comprises llllXlIlg together a molar p equivalent of a phosphorus halogen compound of the I l 5 formula RO-POCHP-OCHPR 30px M. i ii. i 1'. i,

wherein R is selected from the class consisting of alkyl, wherein R is selected from the class consisting of alkyl,

haloalkyl, haloalkenyl, alkoxyhaloalkyl and phenoxyhaloalkyl radicals of from 1 to 12 carbon atoms, R is selected from the class consisting of OR monocyclic and aromatic hydrocarbon radicals of from 6 to 12 carbon atoms, X is selected from the class consisting of chlorine and bromine, at least a molar equivalent of an aldehyde of the formula Wherein Z is selected from the class consisting of hydro gen and alkyl, alkenyl, aryl, alkylthioalkyl and carboalkoxyalkyl radicals of from 1 to 17 carbon atoms and the furyl radical, and less than a molar equivalent of an ester of the formula R' P-OR wherein R and R are as herein defined.

10. The method of preparing the compounds defined in claim 1 which comprises contacting a compound of the formula ROPOCHi R' is 2 1'1 wherein R is selected from the class consisting of alkyl, haloalkyl, haloalkenyl, alkoxyhaloalkyl and phenoxyhaloalkyl radicals of from 1 to 12 carbon atoms, R is selected from the class consisting of OR monocyclic and aromatic hydrocarbon radicals of from 6 to 12 carbon atoms, and Z is selected from the class consisting of hydrogen and alkyl, alkenyl, aryl, alkylthioalkyl and carboalkoxyalkyl radicals of from 1 to 17 carbon atoms, and the furyl radical, with a phosphorohalidite of the formula RO-P-X where R and R are as herein defined and X is selected from the class consisting of chlorine and bromine, and at least an equimolar quantity with respect to the phosphorohalidite of an aldehyde of the formula ZCHO where Z is as herein defined.

11. The method of preparing the compounds defined in claim 2 which comprises contacting substantially two moles of phosphorus trichloride with more than four but less than five moles of an oxirane compound of the formula YCHCHY in which Y is selected from the class consisting of hydrogen, alkyl, haloalkyl and alkenyl radicals of from 1 to 6 carbon atoms, and alkoxyalkyl and phenoxyalkyl radicals of from 2 to 7 carbon atoms and in which the sum of the carbon atoms in the two Y radicals is not more than 10 to obtain a mixture of a phosphorochloridite of the formula l t (CICHCHOhPCl in which Y is as herein defined, and a phosphite of the formula I l (ClCHCHO);P

wherein Y is as herein defined, said phosphite being present in said mixture in a quantity less than equimolar 30 with respect to said phosphorochloridite, and contacting said mixture with at least an equimolar amount with respect to the phosphorochloridite of an aldehyde of the formula H CH wherein Z is selected from the class consisting of hydrogen and alkyl, alkenyl, aryl, alkylthioalkyl and carboalkoxyalkyl radicals of from 1 to 17 carbon atoms and the furyl radical.

12. The method of preparing the compounds defined in claim 3 which comprises contacting two moles of phosphorus trichloride with more than four but less than five moles of propylene oxide to obtain a mixture of bis(2 chloropropyl) phosphorochloridite and tris(2- chloropropyl) phosphite wherein the phosphorochloridite is in molar excess with respect to the phosphite, and contacting said mixture with at least an equimolar quantity, with respect to the phosphorochloridite, of an aidehyde of the formula alk-CHO wherein alk denotes an alkyl radical of from 1 to 17 carbon atoms.

13. The method of preparing the compounds defined in claim 4 which comprises contacting two moles of phosphorus trichloride with more than four but less than five moles of propylene oxide to obtain a mixture of bis(2-chloropropyl) phosphorochloridite and tris(2-chloropropyl) phosphite wherein said phosphorochloridite is in molar excess with respect to said phosphite and contacting said mixture with at least an equimolar quantity with respect to the phosphorochloridite of acetaldehyde.

14. The method of preparing the compounds defined in claim 5 which comprises contacting two moles of phosphorus trichloride with more than four but less than five moles of ethylene oxide to obtain a mixture of bis(2- chloroethyl) phosphorochloridite and tris(2-chloroethyl) phosphite wherein said phosphorochloridite is in molar excess with respect to said phosphite and contacting said mixture with at least an equimolar quantity, with respect to the phosphorochloridite, or acetaldehyde.

15. The method of preparing the compounds defined in claim 6 which comprises mixing together a substantially molar quantity of diethyl phosphorochloridite, a substantially molar quantity of acetaldehyde and less than a molar quantity of triethyl phosphite.

16. The method of preparing the compounds defined in claim 7 which comprises contacting two moles of phosphorus trichloride with more than four but less than five moles of epichlorohydrin to obtain amixture of bis(2,3- dichloropropyl) phosphorochloridite and tris(2,3-dichloropropyl) phosphite wherein said phosphorochloridite is in molar excess with respect to said phosphite, and contacting said mixture with at least an equimolar quantity, with respect to the phosphorochloridite, of acetaldehyde.

References Cited in the file of this patent UNITED STATES PATENTS 2,634,288 Boyer et al Apr. 7, 1953 2,857,415 Birum Oct. 21, 1958 2,890,947 Annable et al. June 16, 1959 2,897,071 Gilbert July 28, 1959 STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,014,954 7 December 26, 1961 Gail H. Birum It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 5 to 13, the lower right-hand portion of the formula should appear as shown below instead of as in the partent:

column 4, lines 55 to 61, the upper portion of the formula should appear as shown below instead of as in the patent:

o 0on o CH ClCH O-P Cl CH POCH-P(OCH CH CH CH3 C H5 )CH3 CH2CH3 column 5, line 72, for "O.,95::l:l..O5 read 03521005 column 23, lines 23 to 26, the formula should appear as shown below instead of as in the patent:

' OCH-P at o (CH2:CHCI-IClCH O) P CH :CHCHClCH O n column 27, line 40, for "rountine" read routine column 28, lines 1 and 2, strike out "alkoxyalkyl, aryloxyalkylj;

lines 54 to 57, the formula should appear as shown below instead of as in the patent:

F I? 1 T? (CH ClCHClCH O) P OCHT ocn- (ocn cuclcn cn CH ClCHClCH O Signed and sealed this 11th day of December 1962.,

(SEAL) Attest:

ERNEST w. SWIDER Attesting Officer DAVID L. LADD Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N00 3,014,954 December 26 1961 Gail H. Birum It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 2, lines 5 to 13, the lower right-hand portion of the formula should appear as shown below instead of as in the partent:

ROP

column 4 lines 55 to 61 the upper portion of the formula should appear as shown below instead of as in the patent:

o 0on o 'ca clca o-f cl on llOCI-l-P(OCH CH CH2CH3 C6H5 OCH3 CH2CH3 column 5, line 72 for "O.95:l:l.O5" read 0095:1005

I column 23, lines 23 to 26 the formula should appear as shown below instead of as in the patent:

0 II P ((3H2=CHCHClCH O) P I OCH- (OCH CHClCI-l=CI-I CH =CHCHClCH2O v n column 27,, line 40 for "rountine" read routine column 28 lines 1' and 2, strike out "alkoxyalkyl, aryloxya1kyl,";

lines 54 to 57, the formula should appear as shown below instead of as in the patent;

(IJH H CH3 0 (CI-I ClCHClCH O) P ocH-1| OCHP(OCH CHClCH C1) cn clcaclcn o Signed and sealed this 11th day of December 1962,

(SEAL) Attest:

ERNEST we. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A COMPOUND OF THE FORMULA
 10. THE METHOD OF PREPARING THE COMPOUNDS DEFINED IN CLAIM 1 WHICH COMPRISES CONTACTING A COMPOUND OF THE FORMULA 